Aba block polymers of polyester and polyethers

ABSTRACT

THE INVENTION RELATES TO NOVEL, SOLID, SUBSTANTIALLY WATERINSOLUBLE ABA BLOCK POLYMERS IN WHICH A BLOCKS COMPRISES RECURRING LINEAR UNITS OF THE FORMULA   -(O-R&#39;&#39;-O-CO-R-CO)-   WHEREIN THE SUBSTITUENTS R AND R&#39;&#39; ARE DIVALENT ALIPHATIC GROUPS AND IN WHICH THE B BLOCK COMPRISES RECURRING OXYALKYLENE UNITS. THE BLOCK POLYMERS HAVE UTIILIITY AS PLASTICIZERS FOR POLYVINYL CHLORIDE RESINS AND AS DYE ASSISTS FOR POLYPROPYLENE FIBER.

United States Patent Int. Cl. C08g 39/10 U.S. Cl. 260-873 3 ClaimsABSTRACT OF THE DISCLOSURE The invention relates to novel, solid,substantially waterinsoluble ABA block polymers in which the A blockscomprise recurring linear units of the formula F u L-OR OCRCUl whereinthe substituents R and R are divalent aliphatic groups and in which theB block comprises recurring oxyalkylene units.The block polymers haveutility as plasticizers for polyvinyl chloride resins and as dye assistsfor polypropylene fiber.

This is a division of application Ser. No. 102,924, filed Dec. 30, 1970,now U.S. Pat. 3,725,352 issued Apr. 3, 1973.

This invention relates to novel, solid, substantially water insolubleABA block polymers in which the A blocks comprise recurring linear unitsof the formula wherein the variables R and R are divalent aliphaticgroups and in which the B block comprises recurring oxyalkylene units.In one aspect, the invention is directed to novel shaped and moldedarticles such as fibers and yarns which comprise polyalkenes and theaforesaid novel ABA block polymers.

The novel blockpolymers which are obtained by the practice of theinvention possess an ABA structure and comprise:

(1) A blocks or segments having the recurring unit represented below:

wherein R is a divalent aliphatic hydrocarbon or aliphaticoxahydrocarbon radical most suitably containing from 2 to 20 carbonatoms, wherein R is a divalent aliphatic hydrocarbon radical mostsuitably containing up to 20 carbon atoms, and wherein said A blocksrepresent from about 15 to about 85 weight percent, preferably fromabout 30 to about 70 weight percent, based on the weight of the ABAblock polymer;

(2) A B block or segment having the recurring unit shown below:

(II) toxyalkylene) wherein the alkylene moiety thereof most suitablycontains from 2 to 5 carbon atoms; and wherein said B block representsfrom about 85 to about 15 weight percent, preferably from about 70 toabout 30 weight percent, based on the weight of the ABA block polymer;

3,825,620 Patented July 23, 1974 ice (3) Wherein the terminal oxy (O-)moiety of the B block is monovalently bonded to the terminal carbonylmoiety of one of the A blocks to form an oxycarbonyl group and whereinthe terminal alkylene moiety of the B block is monovalently bonded to anmy group which in turn is monovalently bonded to the terminal carbonylmoiety of the other A block to thus form an oxycarbonyl p;

(4) Wherein the average molecular weight of the B block is at leastabout 1,000, desirably from about 3,000 to about 50,000, and preferablyfrom about 5,000 to about 25,000; and

(5) Wherein the average molecular weight of the ABA block polymer is atleast about 2,000, desirably from about 4,000 to about 80,000, andpreferably from about 6,000 to about 60,000.

With further reference to the structure designated as Unit I above, itis preferred that R be an alkylene or an oxaalkylene radical of 2 to 10carbon atoms such as ethylene, propylene, butylene,2,Z-dimethyltrimethylene, hexylene, 3-oxypentylene, 3,6-dioxaoctylene,and the like; and that R be an alkylene radical of 1 to 10 carbon atomssuch as methylene, ethylene, propylene, butylene, hexamethylene,octamethylene, and the like.

With reference to Unit II above, it is preferred that the alkylenemoiety thereof contain from 2 to 3 carbon atoms as illustrated byethylene, propylene, and mixtures thereof.

It should be noted that the substantially linear polymeric chain of theABA block polymer can be interspersed with other moieties or groups suchas the urethane group,

the monoand polyaromatic rings including fused and bridged rings such asphenylene, tolylene, biphenylene, naphthylene,phenylene-alkylene-phenylene, phenylenealkylidene-phenylene; ureylene;etc. Such groups, if present, represent but a relatively small weightpercent of the novel ABA block polymer. The terminal hydroxyl orcarboxyl end groups of the novel block polymers, if desired, can befurther reacted with carboxylic acids, anhydrides, isocyanates,epoxides, etc., thus resulting in block polymers which are terminatedwith groups such as alkoxy, e.g., methoxy, butoxy, octoxy, dodecoxy,etc.; the unit f Rewherein the R variable has the significance noted inUnit I supra; the unit i i ROCRC- wherein both R variables have thesignificance stated in Unit I supra; and so forth.

The novel block polymers can be prepared by reacting a polyoxyalkylenediol preferably having an average molecular weight of at least about1,000, desirably from about 3,000 to about 50,000, and preferably fromabout 5,000 to 25,000, with a dicarboxylic acid or anhydride. and aglycol. Though the reaction can be effected noncatalytically, it isdesirable to employ a conventional esterification catalyst. It isobserved that the stannous dialkanoates and tetraalkyl titanates aresuitable catalysts for this reaction. Specific illustrations includestannous diacetate, stannous dibutanoate, stannousdioctanoate, stannousdi(2-ethylhexanoate), stannous distearate, tetrabutyl titanate, sulfuricacid, and the like.

These catalysts are employed in a catalytically significantconcentration. In general, a catalyst concentration in the range of fromabout 0.0001 and lower, to about 3, and higher, weight percent, based onthe weight of reactants, is suitable. The reaction is conducted at anelevated temperature. In general, a temperature in the range of fromabout 100 C., and lower, to about 250 C. is preferred. The reaction timecan vary from several minutes to several hours, e.g., 48 hours or more,depending upon the correlation of variables such as temperature, choiceof reactants, choice of catalyst, etc.

The reaction is preferably conducted in the liquid phase and under aninert atmosphere, e.g., nitrogen. Water formed by the condensationreaction may be removed by distillation. Most desirably, the operativeconditions are adjusted so as to achieve a practical and commerciallyacceptable reaction rate.

The concentration of the reactants, that is, polyoxyalkylene diol,dicarboxylic acid, and glycol will significantly govern the averagemolecular weight of the two A blocks of the resulting ABA blockpolymeric product. The average molecular weight of the B block will, ofcourse, be equal to the average molecular weight of the polyoxyalkylenediol reactant. To obtain hydroxyl-terminated ABA block polymers onewould employ mole ratios of polyoxyalkylene diol, dicarboxylic acid, andglycol in which the total hydroxyl/carboxyl ratio (OH/COOH) is greaterthan one, e.g., from about 1.05 to about 1.5. Alternatively, to obtaincarboxyl-terminated ABA block polymers, one would use carboxyl/hydroxylratios (COOH/OH) greater than one, e.g., from about 1.05 to about 1.5.Oftentimes, the course of the reaction may be followed by making acidnumber or hydroxyl number determinations, as may be the case.

Glycols which can be employed in the esterification reaction include,for example, ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, 1,2-propylene glycol, dipropylene glycol,1,2-butyle1ie glycol, 1,6-hexanediol, 1,4-butanediol,2,2-dimethyl-1,3-propanediol, and the like. Suitable dicarboxylic acidsinclude oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid, theiranhydrides, and the like. Mixtures of glycols as well as mixtures ofdicarboxylic acids can be employed. If desired, carboxyl-terminatedpolyesters can be prepared by reacting predetermined amounts ofdicarboxylic acid and glycol (in which COOH/OH is greater than one) inaccordance with known procedures. The resulting carboxyl-terminatedpolyesters can then be reacted with the polyoxyalkylene diol reactantusing a mol ratio of said polyester to said diol equal to approximatelytwo to prepare the novel ABA block polymers.

The polyoxyalkylene diols which are useful in the process to prepare thenovel ABA block polymer are commonly produced by the polymerization ofan alkylene oxide having terminal epoxy groups such as ethylene oxide,propylene oxide, butylene oxide, etc., or an aliphatic or aromaticcompound having two primary hydroxyl groups. Such compounds includeethylene glycol, propylene glycol, butylene glycol, diethylene glycol,bis (Z-hydroxyethoxy)benzene, 1,4-cyclohexanediol, 2,2-bis(4-hydroxyphenyl)propane, and the like. Preferred polyoxyalkylene diolsare shown by the following formula:

HO (R"CgH3O n wherein R" is hydrogen or lower alkyl of 1 to 3 carbonatoms, and wherein n is an integer such that the average molecularweight of the polyoxyalkylene diol chain is at 4 least 1,000, desirablyfrom about 3,000 to about 50,000, and preferably from about 5,000 toabout 25,000.

In one suitable embodiment, the B block or segment of the novel ABAblock polymer represents the product of the reaction of apolyoxyalkylene diol which has an average molecular weight of from about1,000 to about 15,000, preferably from about 2,000 to about 10,000, witha diglycidyl diether of a dihydric phenol, preferably of abis-(4-hydroxyphenyl)alkane such as 2,2-bis(4-hydroxyphenyl)-propane, ata concentration of from about 1.2 to about 1.5 moles of saidpolyoxyalkylene diol per mole of said diglycidyl diether compound, saidB block having an average molecular weight of from about 3,000 to about45,000, preferably from about 6,000 to about 30,000. Particular suitablepolyoxyalkylene diols are 'those in which the oxyalkylene moiety isoxyethylene,

oxypropylene, oxyethyleneoxypropylene.

The novel block polymers have a myriad of important uses. They can beused as plasticizers for polyvinyl chloride resins; as additives in tapejoint compounds to improve drying characteristics; as surfactants, andthe like.

Greatly improved dyeability has been observed quite unexpectedly, forshaped and molded articles, e.g., yarns, fibers, films, tapes, slitfilms, etc., which are formed from a blend of the novel ABA blockpolymer and synthetic polymer such as the crystalline olefin polymers,e.g., polyethylene, polypropylene, polybutene, poly(4-methylpent-l-ene),and the like; the acrylonitrile polymers, e.g., polyacrylonitrile,polymethacrylonitrile, and the like; the vinyl chloride copolymers,e.g., vinyl chloride/acrylonitrile copolymer, and the like; thecellulosic esters such as the cellulose acetates, the cellulosepropionates, and the like; poly( ethylene terephthalate); and the like.This high absorption capacity for dyes, especially premetallized dyes,is achieved without any noticeable decrease in the mechanical propertiessuch as tensile strength, modulus, elongation, and the like. Forexample, polyolefin fibers produced from blends of polyolefin and thenovel ABA block polymer exhibit mechanical properties which aresubstantially the same as those obtained from the prevailing crystallinepolyolefin per se but have improved dyeability, a higher moistureabsorption capacity, etc.

The aforesaid blends are readily made by blending the selected amountsof ABA block polymer and synthetic polymer with the application of heatand/or pressure in any suitable apparatus. It is usually necessary toapply sufficient heat to raise the polymers above their melting points.Suitable temperatures to be employed in blending the polymers are, forexample, approximately C. and higher, but not so high that significantdecomposition of the polymers or other ingredients takes place.Temperatures as high as 180 C. to about 200 C. can be employed, ifdesired, although lower temperatures are usually suitable andeconomically preferred.

Suitable equipment for blending the polymers together include Banburymixers, screw extruders, two-roll mills, etc. The time of blending orfluxing is not narrowly critical and a sufiicient blending time toobtain a substantially uniform blend is usually satisfactory.

Illustrative times of blending are in the range of from about 1 or 2minutes to 30 minutes or an hour. In the usual case, about 5 to 15minutes is adequate. If desired, other materials can be added duringblending operation such as plasticizers, antioxidants, lightstabilizers, heat stabilizers, etc., and are of the usual types and areused in the usual amounts employed in alkene polymers such aspolyethylene.

Thus, in a preferred embodiment, the invention relates to novel shapedand molded articles such as fibers, yarns, filaments, staple, tow, slitfilm, woven cloth, etc., which have improved dyeability characteristicsand which are formed by blending a synthetic polymer such as acrystalline olefin polymer exemplified previously with/withoutcellulosics plus the novel ABA block polymer. In addition, differentialdyeing can be accomplished by piece dyeing goods such as carpets andupholstery which are woven from unmodified fiber and a fiber previouslyblended with the novel ABA block polymer. Shaped and molded articlescontaining up to about 15 weight percent of ABA block polymer, based onthe total weight of ABA block polymer and synthetic polymer such asolefin polymer, can be dyed to deep and vivid shades of color. Ingeneral, from about one to about 12 weight percent of ABA block polymerin the shaped and molded articles comprising the crystalline olefinpolymer and ABA block polymer can be dyed to a depth of color equivalentto that of wool dyed under similar conditions.

In a second preferred embodiment, the invention relates to novel shapedor molded articles having improved dyeability characteristics formedfrom a blend of crystalline olefin polymer such as polypropylene, novelABA block polymer, and a dye assistant, preferably poly(vinyl pyridine).Additional dye assistants which can be employed include, for example,poly(vinyl pyrrolidone), poly(acrylic acid), and poly(ethyleneimine).These dye assistants can be added to the blend of solid olefin polymerand novel block polymer in an amount up to about weight percent, andhigher based on the total weight of the aforementioned two polymers.

The molded and shaped articles of the instant invention can be dyed byvarious methods. For example, the polymeric blends which make up theshaped and molded articles can be dyed in bulk form or else initiallysha ed into articles such as fibers achieved by spinning techniques andthen dyed. These techniques are conventional in the art as shown in, forexample, US. Pat. No. 3,312,755. The amount of dye which is used is thatamount necessary to impart the desired shade of color. The shaped andmolded articles of the instant invention can take up dyes in amounts upto about 5 weight percent, and higher. based upon the weight of thepolymeric blend, but in many instances less than one to about 5 weightpercent dye solution is generally sufficient to impart the desired shadeof color.

The dyes which can be used with the shaped and molded articles includeacid, disperse, basic, and premetallized dyes. It is especially withpremetallized and disperse dyes that deep and vivid colors are, quiteunexpectedly, obtained. Moreover, the afiinity of such dyes to theaforesaid blends is achieved, as indicated above, without noticeable ordetrimental elfect on the properties of the shaped article, e.g.,fibers, such as secant modulus, tensile strength, elongation, and thelike.

Illustrative dyes are enumerated hereinafter. It is understood that thenotation C.I. followed by a number refers to the Color Index assigned todyes originally by the British in 1924 and subseuently updated in anattempt to specifically characterize dyes where possible. Other dyes canbe found listed in the Encyclopedia of Chemical Technology, pages327-445, Interscience Publisher, (1950). Among the premetallized dyesinclude, for instance, Cibalan Yellow GRL, Cibalan Yellow 2BRL, CibalanYellow FGL, Cibalan Brown 2GL, Cibalan Scarlet GL, Cibalan Red 2GL,Cibalan Orange RL, Cibalan Blue FBL, Cibalan Blue BL, Cibalan Blue BRL,Cibalan Blue 3GL, Capracyl Yellow GW, Capracyl Red G. Typical acid dyesare Formyl Violet S43 (0.1. 698), Martins Yellow (Cl. 9), Fast Red A(Cl. 176), Milling Orange (Cl. 274), Naphthol Green B (Cl. 5), WoodGreen S (Cl. 737), Patent Blue A (CI. 714), Violamine R (Cl. 758),Alizarin Saphinol B (Cl. 504), Alizrin Red S (C1. 1034) Grumpsall Yellow(Cl. 197), Diamond Black F (Cl. 229), Callocyanine (Cl. 833), EriochromeAzrol B (Cl. 720), Naphthol Green Y (Cl. 2), Naphthazarin (CL 1019),Coerulein (C.I. 783), and Solid Yellow 2G. Exempliary basic dyes areRhodamine B (CI. 749), Auramine (CI. 655), Crystal Violet (Cl. 681),Safranine (Cl. 841), Methylene Blue (Cl. 922), Nile Blue A (Cl. 913),Acridine Orange NO (0.1. 788), Sevron Blue 5G (CI. 51004), and SevronRed GL. Disperse dyes can be typified by Celliton Fast Red GGA (CI.11210), Celliton Fast Black BA, and Du Pont Victoria Green.

Of course, various additives such as carriers can be contained in thedye bath in order to secure a more rapid dyeing operation. The additivewill be dependent upon the type of dye used and the selection is wellwithin the ability of those skilled in this art.

The following Examples are illustrative. Unless otherwise specified, allpercentages and parts are by weight.

The term reduced viscosity, as is well known, is a value which also canbe obtained by dividing the specific viscosity by the concentration ofpolymer in the solution, the concentration being measured in grams ofpolymer per milliliters of solvent. The specific viscosity is obtainedby dividing the difference between the viscosity of the solution and theviscosity of the solvent by the viscosity of the solvent. Unlessotherwise noted, the reduced viscosity values herein referred to aremeasured at a concentration of 0.2 gram of polymer in 100 milliliters ofbenzene (or other common organic solvent such as cyclohexanone, toluene,chloroform, etc.) at 30 C.

The novel ABA block polymers prepared in accordance with the teachingsdisclosed herein are substantially water-insoluble, that is to say, notmore than 25 weight percent of a given specimen of ABA block polymer canbe dissolved in water maintained at 95 C. for one hour.

Crude fibers were prepared by blending a general purpose crystallinepolypropylene having a melt fiow of 12.0 and a Melt Index range of 5-50at a temperature range of to 300 C. and the novel block polymer on a tworoll mill for several minutes, e.g., 5 to 60 minutes, at an elevatedtemperature, e.g., about 140 to 180 C. During the milling operation,about 0.5 weight percent of both ultra-violet and thermal stabilizers,i.e., diphenylpenta erythritol diphosphite and2-(2'-hydroxy-3,5'-di-tert butyl)-5-chlorobenzaltriazo (Tinuvin 327),were added. The cooled mill stock was then shaved with an electric drilland a 'fi -inch Speed Bore bit to prepare crude fibers for dyeingstudies. The crude fibers were placed in the dye baths and dyed in aboiling water bath for one hour. After this period of time the fiberswere separated by filtration, washed, and then scoured. The scouring wasaccomplished by placing the dyed fibers in about 50 milliliters ofdistilled water that contains one milliliter of a one percent aqueoussoda ash solution and one milliliter of one percent aqueous nonionicsurfactant solution such as those prepared by the ethoxylation of a C -Clinear alkanol with about 7 moles of ethylene oxide. The amounts of thevarious components of the scouring bath are per gram of fiber. Thefibers were then scoured for 15 minutes in a boiling water bath,filtered, dried and the color evaluated.

The dye solutions employed to dye the aforesaid crude fibers are asfollows:

(i) When disperse dyestuffs are employed.For each gram of fiber, 5milliliters of a one percent aqueous dye solution and 0.5 milliliter ofnonionic surfactant are added to about 50 milliliters of distilledwater.

(ii) When acid dyestufis are employed.For each gram of fiber, 5milliliters of a one percent aqueous dye solut on, 4 milliliters of anaqueous two percent H 50 solution, and 0.5 milliliter of a nonionicsurfactant are added to about 50 milliliters of distilled water.

(iii) When premetallized dyestuffs are employed.For each gram of fiber,5 milliliters of one percent aqueous dye solution, 2 milliliters of anaqueous 2 percent DAP solution and 0.5 milliliter of a nonionicsurfactant are added to about 50 milliliters of distilled water.

(1v) Basic dystutfs are employed.For each gram of fiber, 5 millilitersof a one percent aqueous dye solution and 0.5 milliliter of a nonionicsurfactant are added to about 5 0 milliliters of distilled water.

The nonionic surfactant employed in the above dye solutions are preparedby the ethoxylation of C C linear alkanols with about 12 moles ofethylene oxide.

7 EXAMPLES 14;

Various novel ABA block polymers were prepared in accordance with thefollowing procedure. The polyethylene diol, dicarboxylic acid, andglycol were charged to a glass reaction vessel.

The system was flushed with nitrogen and the reaction mixture wasmaintained under reduced pressure, e.g., about 1 mm. of Hg, to thusremove water formed as a 8 mal stabilizer (0.1 gram) were added to theblend during the milling operation. Milling behavior regarding fluxing,banding, bank, roll, release, dispersion, and hot strength weredescribed as good. Crude fibers were then prepared, then separately dyedwith Capracyl Red B, Xylene Milling Blue BL, Sevron Blue 5G, andCelliton Fast Red GGA, and finally scoured as described previously.Results are set out in Table III below:

TABLE III.RESULTS OF DYEING AND SCOURING CRUDE FIBERS ABA block Cellitonpolymer, Capraeyl Xylene Fast Red Example Example Red B; pre- MillingBlue Sevron Blue GGA; number Number metallized BL; acid 5G; basicdisperse 1 Medium red... Medium blue. Medium blue Deep red. 2 Deep redDeep blue .do D0. Do. Do. Do. Do. Do. Do.

1 ABA Block Polymer prepared in accordance with the procedure set out inExamples EXAMPLE 25 To a reaction vessel containing 1000 grams of apolyoxyethylene diol having an average molecular weight of approximately6000 heated to about 65 C. in a nitrogen atmosphere, there were added8.87 grams of aqueous 50 percent sodium hydroxide solution. Theresulting admixture was stirred until solution resulted. Thereafter a109 gram portion of this solution was transferred to another vessel andheated to 95 C. in a nitrogen atmosphere, and 2.88 grams of diglycidylether of 2,2-bis(4-hydroxyphenyl)propane were quickly added, withstirring. This TABLE I Reduced Yield of viscosity Polyoxy ABA of ABA.Example Dicarboxyhc Wt. of Wt. of ethylene Wt. of polymer, polymer,number acid acid Glycol glycol 1 diol diol 1 percent dljgm.

4. 8 1,6-hexaucdiol 4. 7. 50 06 0. 00 3. 0 1,10-decamethylenediol 4. e7. 50 0. 14 3.9 do 4.6 7.50 07 0.10 5. 1 Diethylene glycol. 3. 7 7. 5007 0. 05 5. 1 do 3. 7 7. 50 05 0. 04 4. 3 1,10-decamethylenediol. 4. 07. 50 07 0. 18 7 0 5. 2 1,6-heXanedi0l 3. 3 7. 50 07 0. l8 8 Succiuicacid 4. 2 2,2-dimethyl-1,3-propancdi0l 4.0 7. 50 97 0. 11

1 Weight of reactant is in grams.

2 Polyoxyetliylenediol having an average moleclar weight of about 6,000.

3 Polyoxyethylenediol having an average molecular weight of about 3,000.

4 Reduced viscosity values were determined in benzene at 30 C. using aconcentration of 0.2 dl./gm.

EXAMPLES 9-17 To test the dyeability of crystalline polypropylenewithout the novel block polymers as dye assistants, 20 parts ofpolypropylene was milled wtih 0.1 part UV stabilized and 0.1 partthermal stabilizer on a two-roll mill for five minutes at 170 C. Millingbehavior was described as good. Crude fibers were then prepared and dyedand scoured as noted in the procedure prior to the Examples. The resultsare set out in Table II below:

TABLE II Example Type number Dyestuff dyestufi Color 9 Celliton Fast RedG GA Disperse Red tint. 10 I atyl Orange 3R do Orange tint. 11 EastmanFast Yellow GLF do 12- Eastman Polyester Red 2G "do Red tint. 13Capracyl Red B Premetalized No color. 14..-. Xylene Milling Blue BL AcidDo. 15 Du Pont Milling Red do Do. 16- Amacid Milling Brown d Do. 17Sevron Blue 5G Basie Do.

EXAMPLES 18-24 Eight blends were prepared by mixing 90 parts ofcrystalline polypropylene and 10 parts of each of the eight blockpolymers of Examples 1-8 supra. The blending operation was conducted ona two-roll mill for 15-25 minutes at 170 C. Ultraviolet stabilizer (0.1gram) and theramount corresponds to a molar ratio of 0.5:1 of thediglycidyl ether to the polyoxyethylene diol. Thereafter the temperaturewas held within the range of C. to C. for 40 minutes, and the reactionmixture was allowed to cool to room temperature and solidify. The solidmaterial was a tan-colored wax which melted at 60 C. A solution of 50grams of this material in grams of water contained only traces of geland had a viscosity at 30 C. of 913 centipoises.

EXAMPLE 26 EXAMPLE 27 (A) Example 1 was repeated except that 10 grams ofthe polyether product of Example 26 were employed. There was obtained asolid ABA block polymer.

(B) Ninety parts of crystalline polypropylene, 10 parts of the novel ABAblock polymer of paragraph (A) above, 0.005 part UV stabilizer, and0.005 part thermal stabilizer were blended on a two-roll mill at 170 C.for 5 to 10 minutes. All aspects of the milling operation were rated asgood. From these blends, crude fibers were prepared, dyed and scoured asdescribed previous. The dye was Capracyl Red B, a premetallized dye. Thecrude fibers dyed to a deep red.

EXAMPLE 28 (A) Example 4 was repeated except that 8 grams of thepolyether product of Example 27 were employed. There was obtained asolid ABA block polymer.

Ninety parts of crystalline polypropylene, 10 parts of the novel ABAblock polymer of paragraph (A) above, 0.005 part thermal stabilizer wereblended on a two-roll mill at 170 C. for about 10 minutes. All aspectsof the milling operation were rated as god. From these blends, crudefibers were prepared, dyed and scoured as described previous. The dyewas Capracyl Red B, a premetallized dye. The crude fibers dyed to a deepred.

What is claimed is:

1. Shaped and molded article of manufacture of improved dyeability withdispersed dyes, premetallized dyes, basic dyes and acid dyes containinga polymer blend of up to about 15 weight percent of a solid blockpolymer possessing an ABA structure therefor consisting essentially of:

(i) A blocks having the recurring unit shown below:

O layout} wherein R is of the group consisting of an aliphatichydrocarbon radical having from 2 to 20 carbons and an aliphaticoxahydrocarbon radical having up to 20 carbon atoms, wherein R is adivalent aliphatic hydrocarbon radical having up to 20 carbon atoms, andwherein said A blocks represent from about 15 to about 85 weight percentof said ABA block polymer; (ii) a B block having the recurring unitshown below:

toxyalkylene) wherein the alkylene moiety contains from 2 to 5 carbonatoms, and wherein said B block represents 10 from about to about 15weight percent of said ABA block polymer; 9

(iii) wherein the terminal oxy moiety of the B block is monovalentlybonded to the terminal carbonyl moiety of one of the A blocks to form anoxycarbonyl group, and wherein the terminal alkylene moiety of the Bblock is monovalently bonded to an oxy group which in turn ismonovalently bonded to the terminal carbonyl moiety of the other A blockto thus form an oxycarbonyl group;

(iv) wherein the average molecular weight of the B block is at leastabout 1,000;

(v) wherein the average molecular weight of the ABA block polymer is atleast about 2,000, and the balance thereof being a solid olefin polymer.

2. The shaped and molded article of manufacture of claim 1 wherein saidsolid olefin polymer is crystalline polypropylene; wherein the B blockof said solid copolymer has an average molecular weight of from about3,000 to about 50,000, wherein the average molecular weight of the ABAblock polymer is from about 4,000 to about 80,000, the R substituent isof the group alkylene and oxaalkylene, each having from 2 to 10 carbonatoms, and R is alkylene of from 1 to 10 carbon atoms, and wherein saidsolid block copolymer is used in an amount ranging up to about 15 weightpercent, based on the total weight of said solid olefin polymer and saidsolid block polymer; and wherein said dye is of the group consisting ofdispersed dyes, premetallized dyes, basic dyes, and acid dyes.

3. The shaped and molded article of manufacture of claim 2 wherein thealkylene moiety of the oxyalkylene unit is of the group consisting ofethylene, propylene, and mixtures thereof.

References Cited UNITED STATES PATENTS 3,652,713 3/ 1972 Okazaki 260-8603,410,927 11/1968 Crovatt, Jr. 260-860 3,359,344 12/1967 Fukushima260-8733 WILLIAM H. SHORT, Primary Examiner T. E. PERTILLA, AssistantExaminer US. Cl. X.R.

